Bromide-chloride salt moisture indicating composition



Dec. 22, 1970 w. o. KRAusE BROMIDE-CHLORIDE SALT MOISTURE INDICATING COMPOSITION original Fiied Aug. 19, 196s 3 Sheets-Sheet 1 i mofa-ff MAW/ts ff? /v/Z//an/ 4 .l l n Dec. 22, 1970 w. o. KRAUSE 3,548,639

BROMIDE-CHLORIDE SALT MOISTURE INDICATING COMPOSIT\` 3 Sheets-Sheet 2 Original Filed Aug. 19, 1968 Dec. 22, 1970 w. o. KRAusE 3,548,639

BRCMIDE-CHLORIDE SALT MOISTURE INDICATING COMPOSITION Original Filed Aug. 19. 1968 `3 Sheets-Sheet 3 United States Patent Office 3,548,639 Patented Dec. 22, 1970 ABSTRACT OF THE DISCLOSURE Moisture-indicating materials of the type used in refrigerant systemsto detect moisture content which may have a deleterious effect upon the system capabilities, particularly a mixed salt consisting of cobaltous bromide and either barium chloride or magnesium chloride. The

moisture indicator composition undergoes a reversible color change as wetted, indicating the degree of moisture within the refrigerant system.

ACRoss inFERENCEs To RELATED APPLICATIONS A division of Dual-Salt Moisture-indicating Composition (Ser. No. 753,655), filed Aug. 19, 1968, now Pat. No. 3,499,316, Mar. 10, 1970.

BACKGROUND "OF THE INVENTION (1) Field of the invention In refrigerant systems and related liquid systems, a great deal of recent attention has been given to the detection of water or moisture content which has a deleterious effect upon .system capabilities. Cobaltous bromide has been employed as an impregnant for glass ber or paper. Cobaltous bromide itself undergoes a dominant color change from green to pink, as it becomes saturated with water. However, the color change of cobaltous bromide is fairly finite with respect to the percentage of water detected, that is the cobaltous bromide rapidly completes its color change within a narrow percentage range of moisture. Accordingly, attention has been given to developing related compositionswhich would have variant color indicating characteristics as system needs dictate.

(2) Description of the prior art Cobaltous bromide moisture indicators may be positioned in a moisture indicator hbusing, of the type illustrated and claimed in Pat. 3,085,424 and assigned to assignee herein. The liquid phase indicator may be of a cobaltous bromide type applied to a mat of inert fibers, as disclosed in Pat. No. 2,836,974 or, as applied to a cellulosic paper, as set forth in Pat. 2,76,3l2. In both cases the color indicators were used in refrigerant systems having a refrigerant liquid of low water solubility.

A principal prior art teaching of the employment of salts such as magnesium chloride, calcium chloride and aluminum chloride together with cobalt chloride is set forth in Applied Biology (M. E. Solomon): The Use of Cobalt Salts as Indicators of Humidity and Moisture, pages 75-85.

SUMMARY OF THE INVENTION According to the present invention the color indicating characteristics of the cobalt salt are considerably varied by employing dual salts such as the following:

(l) cobaltous acetate with another acetate salt;

2 Claims (2) cobaltous bromide with bromiclcs of barium or magnesium; and

(3) dual bromide salt combinations, such as cobaltous bromide and a bromide salt of zinc, cadmium or mercury.

The color change results thus achieved, are illustrated in FIGS. 1, 2, 3, 4, 5, and 6.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. l is a graph depicting approximate color changes by hue of the dual acetate salts: cobaltous acetate and acetate zinc, cadmium and mercury, as affected by water content;

FIG. 2 is a corresponding graph of the dual bromide salts: cobaltous bromide and bromide of zinc, cadmium and mercury;

FIG. 3 is a like graph of the dual bromide salts: cobaltous bromide and bromide of barium, magnesium and cadmium;

FIG. 4 is a graph depicting approximate color change by hue with the increasing of the ratio of cadmium bromide to cobalt bromide;

FIG. 5 is a graph depicting approximate color change by hue with the increasing of the salt concentration;

FIG. 6 is a graph depicting approximate color changes of the cobaltous bromide-cadmium bromide indicator in operating refrigeration units.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Free and dissolved water in refrigeration systems has always been a major problem. The presence of moisture in these systems can lead to some undesirable effects such (l) Chemical reaction with oil or refrigerant to form acidic materials, tars and varnishes.

(2) Clogging of metering devices due to freeze up.

(3) Lowering of the dielectric of motor insulation in hermetic and semihermetic motors resulting in motor failure.

(4) Enhanced probability for copper plating.

As a result, manufacturers of refrigeration equipment as well as the installing contractor and service engineer carry out expensive and/or time consuming procedures to obtain the degree of internal dryness which leads to reliable and prolonged system operation. These procedures generally consist of high vacuum techniques combined with elevated temperatures. However, even when these techniques are followed, the concentration of moisture in the system cannot be specifically determined unless expensive and time consuming analytical techniques are used. Some manufacturers carry out these procedures on a small segment of their daily production to assure themselves that their manufacturing procedures are conforming to expectations. Further, dehydrators containing desiccating materials are installed for further protection.

Since analysis of each assembly is economically unfeasible to the manufacture and impossible for field assembled equipment, moisture indicators have been used. These indicators reversibly change color with changes in relative saturation of water dissolved in a particular refrigerant.

The working portion of these indicators generally consist of a cobalt salt, preferable cobalt bromide, deposited on paper or some other material such as a polyester or fiber glass.

estacas L after the relative saturation reaches about 17%. The

color obtained below 5% relative saturation is considered the dry color while that obtained above 17% is considered the wet color. It is postulated that the cellulosecobalt bromide forms a complex salt with different characteristics than the cobalt salt alone.

When no complex is formed such as a polyester cobalt bromide color changes occur at a lower relative saturation of water in refrigerants. This change occurs at about 1.2 to 2.4% relative saturation with the wet color occurring above 2.4% and the dry color below 1.2% relative saturation. The degree of sensitivity to low dissolved moisture levels is desirable in many cases. This is especially true when proper dehydration of equipment has been carried out. These systems, then, have an extremely low concentration of moisture in the circulating refrigerant when first placed into operation. Later, through normal or but generally adverse operating conditions deterioration of the organic constituents such as oil or motor insulation water is formed and the concentration of dissolved water rises. If deterioration should continue equipment failure will result. Accordingly, a monitoring system such as a moisture indicator changing color at low moisture levels is vital. Should color change occur proper procedure can be taken to correct the adverse conditions. l

IUnder a given set of operating conditions, system sensitivity to chemical or thermal deterioration varies with selection of components making up the motor compressor. Some components are more sensitive than others to the environment and depending upon their chemical nature contribute more or less water to the system during deterioration. The amount of material used also bears on the quantity of water contributed to the system.

Considering moisture increase in a system as an indication of chemical deterioration, a moisture indicator changing from a dry to a wet color would signal that this deterioration is occurring. With syste-ms of varying sensitivities and ability to create water, moisture indicators should lbe designed for specific refrigeration systems. Rather, standardized moisture indicators are applied to any and all systems. By changing the ratio of cobaltous bromide to the paper base the standard indicators can be made to show color shifts between narrow limits.

Indicators can be prepared that will show color changes at high moisture levels or at low moisture levels. This can be done by the addition of water soluble salts of metals in Group II-A and II-B in the periodic table to cobaltous bromide. Furthermore, other cobaltous salts such as the nitrate, acetate and sulfate with cobalt chloride and bromide have a color change shifting effect. Ad-

.ditionof Group II-B salts to the cobaltous bromide or chloride sensitizes the moisture indicatorthat is-color shifts from dry to wet occur at a lower water concentration level. On the other hand, salts of Group II-A have the opposite effect.

By varying the ratio of one salt to another and/or by varying the ratio of salt mixture to the paper base one can obtain moisture indicators, with color shifts in any desired range depending upon the requirements of the refrigeration system `to which it is applied.

The moisture indicators are prepared by immersing unsized paper, such as Whatman No. 1 laboratory grade filter paper in the solution of the salts. The solutions are controlled very specifically with regard to normal concentrations of the salts as well as the ratio of concentration of one salt to another.

After drying the treated paper, the paper can be cut to various geometric configurations to be mounted in a hermetic device having a sight glass and proper fittings for installation in refrigeration systems. The color change of the indicator with changing concentrations of dissolved water inthe refrigerant can be observed through the sight glass.

.Examples of some of the various types of moisture indicator combinations are shown in the graphs FIGS. 1-6. For simplicity purposes the color changes are shown as change by hue rather than specific colors since the dry color is not always at the same hue. For example, the dry color for a cobaltous bromide based indicator has a Color Harmony Value of 15 ic while an indicator prepared with cobalt chloride mercuric chloride has a Color Harmony Value of 121/2l gc in its dry state.

The base line of the graphs is considered as the color -of the indicator in its dry state. This color is generally a blue color. The graph shows the indicator going through its intermediate stages of lavendar, lilac, etc. The termination point of each graph line is that point at which a definite pink or wet color is reached. This is generally equivalent to a Color Harmony Value of 11 l The addition of salts to Group II-B to sensitize these elements appears to eliminate the dry anhydrous colorso that one continuously approaches the intermediate colors with increasing amounts (based on the ratio of the two salts) of the II-B salts. In this way the number of hues the indicator must go through to reach the pink or wet color, is constantly reduced.

The effect of the addition of the dual salts on the color change characteristics of Whatman No. 1 filter paper are set forth in Tables 1-4 below:

TABLE ONE [llticct of the Addition of Various Salts ou the Color Change Characteristics of Whatman No. 1 Filter Paper Treated with Colrg Color Harmony Value No salt added 2nBr2 CdBrz HgBrz MgBrz CaBrz BaBrz LizBr Co(NO3)g Percent; H2O in II-151:

0 151e 13% ec 13% ic 13% ic 1619. 17 la 16 la 161e. 131e 1 151e 13% ec 13% ic 13% ic 161a 1 7 la 16 la 16 la 13 lc 2 151e 13 ec 13% ic 13% ic 16 la 1718l 1619. 16 la 13 ia. 3 15 ic 12% ec 12% ge 12% ge 16 la 17 la 16 la 161e. 13 ic 3 15 1e 12% ec 12% ec 12% ec 16 la. 17 la 16 la 16 la. 13 ic 3 15 te 12% ec 12% ee 12% ee 16 la 17 la 16 la. 16 la 13 ic 3. 15 1c 12 ee 11 ec 11 ec 16 'ia 17 ia 16 ia 16 ia 13 ic 4. 15 ge 12 ec 11 ec 11 ec 16 ia 17 ia 16 ia 16 ia 13 ic 4. 15 ge 11 ca 10 ec 10 ec 16 ga. 17 ga 16 ga 16 ga. 13 ie 5. 15 gc 11 ca. 10 ec 10 ec 16 ga 17 ga 16 ga 16 ga 13 ie 6. 14 ec 7 ca 7 ca 7 ca 16 ga 17 ga. 16 ga 16 ga. 13 go 7. 13ca 7ea Ica I'ca 17 ee 17 ga 16 ec 16 ec 12 ec S. 7 ca. 7- ca 16 ga` 14 ec 14 ec 10 ca 9. 17 ea 13% ca 13 ca 10.00. 17 en 12% ca. l2 ca. 11. 17u11 12e l.' en 1' 14 en. 1". cu. l! en 13. 12% c.; 12 ca 1.'. ea. 14.00 12 ca l2 ca l. ca

TABLE TWO [Effect of the Addition of Various Salts on the Color Change Characteristics of Whatman N o. 1 Filter Paper with Co(Ac)2} Percent H20 Color Harmony Value m H-151 Co(Ac)g Zn(AC) Cd(Ac)3 Hg(Ac)z Co(N03)1 12 ic 11 gc 12 gc 11 ge 11 ic 12 ic 11 gc 12 gc 11 gc 11 ic 12 ga 10 ec 12 gc 11 gc 10 ic 12 ga 10 ec 11 gc 11 ec 10 ic 12 ga. 10 eo 11 gc 11 ec 10 gc 11 go 10 ec 11 ge 11 ec 10 gc 11 gc 10 ec 11 ec 11 eo 10 ge 1l gc 10 ec 11 ec 10 ec 10 gc 11 ec 10 ec 11 ec 10 ec 10 gc 11 ec 10 ec 11 ee 10 ec 9 go 11 ec 10 cb 10 cb 10 ec 9 gc 11 ca 10 cb 10 cb 9 ca 9 ca 11 ca 10 cb 10 cb 9 ca 9 ca TAB LE TH RE E 1.25 CJC; CdBrz H2O, p.p.m. percent 13 gc 5. 8 0.47 13 gc 7. 0; 7. 0; 7. 1 0. 57; 0. 57; 0. 57 13 gc 8. 7; 8. 9; 10.3 0. 70; 0. 72 l2 ec 16. 5; 17. 5; 18. 0 1. 35; 1. 42; 1. 47 12 ca 20. 2; 19. 6; 19. 3 1. 64; 1. 50; 1. 57 11 ic 34. 6; 35. 4; 35. 4 2. 8; 2. 9; 3. 9 11 ca 61. 0; 58. 3; 58.3 5. 0;4. 7;4. 7 ca 61; 64; 64 5. 2; 5. 2; 5. 2

Color calibration of a dual salt system involving cobaltous bromide and cadmium bromide is set forth in Table Four and color change points of this dual salt indicator are set forth in Table Five.

Manifestly, the concentration of the dual salts may be [Effect of Increasing the Ratio of Cadmium Bromide to Cobalt Bromide on the Color Chango Characteristics of Treated Whatman N o. 1 Filter Paper] Color Harmony Value H2O in H-151, Molar Ratio of CoBr: to CdBrz CoBrg-l percent by wt. $6 1 1% 2 3 4 5 14 ie 13% ic 13% ie 13% gc 13% ic 13 io 13 ga 14 gc 13% ic 13% gc 13% gc 13 ic 13 ic 13 ga 14 gc 13)/2 gc 14 ec 14 ec 12% ec 12 ca 12% ga 1215 ec 12 ec 12% ca 12 ea 12% ec 12 ca 12 ca 12 ec 12% ca 7 cb 7 cb 12 ec 12% ca 7 cb 7 cb 12% ca 10 cb 7 cb 7 cb 12% ca 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb 7 cb TABLE FOUR [Efiect oi Increasing the Salt Concentration 1n the Color Characteristics ofWhatman N o. 1 Filter Paper Treated with CoBrg and CdBr2] Color Harmony Value Amount Salt in 100 ca. H10, g.

Percent H2O 5.00 g. CoBr2; 10.00 g. CoBrz; 20.00 g. CoBrr; in H-151 7.85 g. CdBrz 15.70 g. CdBrz 31.40 g. CdBrz 0 1.00- 2.00- 3.00- 3.25. 3.50- 3.75- 4.00. 4.50. 5.00. 6.00 7cb .Qgc 12ga TABLE FIVE [Color Calibration of Dual System Paper Base Moisture Indicators Treated with CoBrg and CdBm C0Br2=0.023M/liter=11 1.00 'H2o, Temp., om, CdBrz p.p.m. F. percent 13% gc 2. e 88 2. 1 13% gc 2. 5 84 2. 3 13 gc 2. 9 84 2. 6 12% ec 3. 6 83 3. 4 11 ec 6. 1 76 7.1 11 ec 11. 5 78 12. 5

132/2 ic 9. 7 74 0. 80 13% gc 10. 5 74 0. 85 12% gc 19. 0 74 1. 54 12% ec 21. 4 74 1. 73 12% ec 22. 0 74 1. 79 12% ec 30. 0 74 2. 46 12 ec 43. 3 74 3. 52 12 ec 48. 0 74 3. 90 11 ce. 57.0 74 4. 62

References Cited UNITED STATES PATENTS 2,460,068 1/1949 Davis 252-408 2,460,069 l/l949 Davis 252-408 2,526,938 10/1950 Davis et al. 252-408 2,761,312 9/1956 Line et al 73-61.1 3,173,880 3/1965 Pappas et al. 73-61.1X

LOUIS R. PRINCE, Primary Examiner I. W. ROSKOS, Assistant Examiner U.S. C1. X.R. 

